Olefin oligomerization process and catalysts therefor

Abstract

The use of novel heterogeneous catalyst complexes as catalysts for oligomerizing alpha-olefins is disclosed. The complexes are formed from (i) a solid olefin polymer having a linear backbone and a plurality of pendant omega-hydroxyalkyl groups, (ii) an organomagnesium halide, and (iii) a boron trihalide, preferably BF.sub.3. The complexes can be recovered and reused repeatedly in batch-type operations and can be used for long periods of time in continuous or semi-continuous operations without replenishment of their boron trifluoride content.

Claims

1. A process of oligomerizing at least one oligomerizable 1-olefin having in the range of about 6 to about 20 carbon atoms per molecule which comprises (a) contacting said 1-olefin with a solid catalyst consisting essentially of a complex formed from (i) a solid olefin polymer having a linear backbone and a plurality of pendant omega-hydroxyalkyl groups, (ii) an organomagnesium halide, and (iii) a boron trihalide, with the catalyst complex at a level of about 0.5% to about 30% by weight of the oligomerizable 1-olefin and at a temperature of about 0.degree. C. to about 80.degree. C. such that a liquid oligomerization product is formed, and (b) separating the liquid oligomerization product from the solid catalyst complex, and (c) re-using the solid catalyst complex from (b) in (a).

2. A process according to claim 1 wherein said organomagnesium halide is a hydrocarbylmagnesium chloride and said boron trihalide is boron trifluoride.

3. A process according to claim 1 wherein said solid olefin polymer used in forming the complex is a poly(1-alkene-co-1-alken-.omega.-ol) polymer in which the alkene units can be the same or different and contain 3 to about 10 carbon atoms each and the 1-alken-.omega.-ol units contain 6 to about 12 carbon atoms each.

4. A process according to claim 1 wherein said oligomerizable 1-olefin is at least one oligomerizable 1-olefin having in the range of about 8 to about 14 carbon atoms per molecule, wherein said solid olefin polymer used in forming the complex is a poly(propylene-co-1-alken-.omega.-ol) polymer in which the 1-alken-.omega.-ol units contain 6 to about 12 carbon atoms each, wherein said organomagnesium halide is a hydrocarbylmagnesium chloride and wherein the boron trihalide is boron trifluoride.

5. A process according to claim 4 wherein said 1-olefin is a linear 1-olefin.

6. A process of preparing alpha-olefin oligomer in a series of two or more separate oligomerization reactions which comprises:

a) conducting a first oligomerization reaction by contacting at least one oligomerizable 1-olefin having in the range of about 6 to about 20 carbon atoms per molecule with a solid catalyst consisting essentially of a complex formed from (i) a solid olefin polymer having a linear backbone and a plurality of pendant omega-hydroxyalkyl groups, (ii) an organomagnesium halide and (iii) a boron trihalide, whereby the oligomerization results in a reaction mixture comprising a liquid alpha-olefin oligomer phase and a solids phase comprising said olefin polymer catalyst residue; with the catalyst complex at a level of about 0.5% to about 30% by weight of the oligomerizable 1-olefin and at a temperature of about 0.degree. C. to about 80.degree. C.;

b) separating said liquid phase and said solids phase from each other; and

c) conducting another said reaction by contacting at least one oligomerizable 1-olefin having in the range of about 6 to about 20 carbon atoms per molecule with said solids phase as the aforesaid catalyst complex, with the catalyst complex at a level of about 0.15% to about 30% by weight of the oligomerizable 1-olefin and at a temperature of about 0.degree. C. to about 80.degree. C.;

7. A process according to claim 6 wherein said organomagnesium halide is a hydrocarbylmagnesium chloride and said boron trihalide is boron trifluoride.

8. A process according to claim 6 wherein said series of separate oligomerization reactions comprises at least 5 successive separate oligomerization reactions in which after the end of each reaction said liquid phase and said solids phase are separated from each other and said solids phase is used together with a fresh charge of at least one oligomerizable 1-olefin having in the range of about 6 to about 20 carbon atoms per molecule in conducting the next oligomerization reaction.

9. A process according to claim 6 wherein in each said separate oligomerization reaction said oligomerizable 1-olefin is at least one oligomerizable 1-olefin having in the range of about 8 to about 14 carbon atoms per molecule, wherein said organomagnesium halide is a hydrocarbylmagnesium chloride, and wherein said boron trihalide is boron trifluoride.

10. A process according to claim 6 wherein said solid olefin polymer used in forming the complex is a poly(1-alkene-co-1-alken-.omega.-ol) polymer in which the alkene units can be the same or different and contain 3 to about 10 carbon atoms each and wherein the 1-alken-.omega.-ol units contain 6 to about 12 carbon atoms each.

11. A process according to claim 6 wherein said oligomerizable 1-olefin in each of said two or more separate oligomerization reactions is at least one oligomerizable 1-olefin having in the range of about 8 to about 14 carbon atoms per molecule, wherein said solid olefin polymer used in forming said complex is a poly(propylene-co-1-alken-.omega.-ol) polymer in which the 1-alken-.omega.-ol units contain 6 to about 12 carbon atoms each, and wherein the boron trihalide is boron trifluoride.

12. A process according to claim 6 wherein said 1-olefin in a) and c) thereof is linear 1-olefin.

13. A process according to claim 6 wherein said solid olefin polymer used in forming said complex is poly(propylene-co-(1-hexen-6-ol).

14. A process according to claim 1 wherein said 1-olefin in a) and c) thereof is linear 1-olefin.

15. A process according to claim 14 wherein said poly(propylene-co-1-alken-.omega.-ol) polymer is poly(propylene-co-(1-hexen-6-ol).

16. A process according to claim 15 wherein said oligomerizable 1-olefin is predominately one or more C.sub.8 -C.sub.12 linear 1-olefins.

17. A process according to claim 10 wherein said series of separate oligomerization reactions comprises at least 5 successive separate oligomerization reactions in which after the end of each reaction said liquid phase and said solids phase are separated from each other and said solids phase is used together with a fresh charge of said oligomerizable 1-olefin in conducting the next oligomerization reaction.

18. A process according to claim 10 wherein said series of separate oligomerization reactions comprises at least 10 successive separate oligomerization reactions in which after the end of each reaction said liquid phase and said solids phase are separated from each other and said solids phase is used together with a fresh charge of said oligomerizable 1-olefin in conducting the next oligomerization reaction, and wherein said oligomerizable 1-olefin is predominately one or more C.sub.8 -C.sub.12 linear 1-olefins.

19. A process according to claim 18 wherein said linear 1-olefin is 1-octene, and wherein said poly(propylene-co-1-alken-.omega.-ol) polymer is poly(propylene-co-(1-hexen-6-ol).

20. A process according to claim 10 wherein said series of separate oligomerization reactions comprises at least 12 successive separate oligomerization reactions in which after the end of each reaction said liquid phase and said solids phase are separated from each other and said solids phase is used together with a fresh charge of boron trifluoride and a fresh charge of said oligomerizable 1-olefin in conducting the next oligomerization reaction, wherein said oligomerizable 1-olefin is predominately one or more C.sub.8 -C.sub.12 linear 1-olefins, wherein said poly(propylene-co-1-alken-.omega.-ol) polymer is poly(propylene-co-(1-hexen-6-ol), wherein said organomagnesium halide is a hydrocarbylmagnesium chloride.